Manufacture of active carbons



Patented Nov. 12, 1929 UNITED STATES PATENT OFFICE EDOUARD URIBAIN, F PARIS, FRANCE, ASSIGNOR T0 URBAIN CORPORATION, A CORYORATION OF DELAWARE MANUFACTURE or ACTIVE cannons No Drawing. Application filed April 24, 1925, Serial No. 25,707, and in France December '24, 1924.

My studies have shown me that in order to produce a highly active carbon it is necessary to fulfill the following conditions:

First: The hydrogen content must be reduced to the minimum attainable;

Second: The compactness must be suitable for the ultimate purposes for which the carbon is to be used; the compactness of a carbon granule bein the ratio of the volume actually occupied y thesolid carbon in that granule to the tota apparent volume of the granule (i. e. the volume of the solid plus the volume of the pores). The compactness may vary over wide limits. For example,

when absorbing light gases I have used a carbon having a compactness of .5; whereas for certain vapours, better results have been obtained with a carbon having a compactness of .25. Under extreme conditions even a 2 wider range may be desirable, and it is. important that the manufacturer be able to control the compactness of the finished product without unduly sacrificing the beneficial qualities arising from a minimum hydrogen p content.

When a vegetable material is calcined under usual conditions, there remains after calcination a considerable quantity of hydrogen; however, by prolonging the calcination and by considerably raising the temperature, and in certain cases by heating under vacuum, it is possible to eliminate the hydrogen, but such operations are not industrially economic and further the compactness of the carbon thus obtained is generally insufiicient for industrial purposes. l I

Oxidation by air, water vapour or combustion ses, was conceived by Ostrejko tolbe capab e of effecting good results, and to a 4 certain extent, does accomplish the desired urpose, as the water va our acts on the residual hydrocarbons and estroys them, forming carbon monoxide and hydrogen. Unfortunately, water vapour or the other gases above mentionedact also during the operation to alarge extent on the carbon, causing a great loss of carbon. That is why, with this process it is diflicult to obtain a sufficiently compact material sufficiently deprived of hydrogen, even if one utilizes only I those vegetable materials, which give a very dense compact charcoal. 7

One phase of my invention is based upon the discovery that carbon can be produced, which is substantially free from hydrogen, and at the same time with sufiicient compactness for the purposes desired, it material such as peat, lignite, ground corozo nuts or the like is permeated with a liquid which is adapted at relatively high temperatures to act rapidly to break down hydrogen containing compounds, and which has relatively little effect on the body of the carbon in the course of the operation, and then, preferably after drying, is heated in a retort or similar apparatus to such temperatures. The temperature may vary with different reagents. Many different substances will serve this purose with varying efiiciency such as'the metallic chlorides, of which zinc chloride mayf serve as an illustration, or a relatively nonvolatile acid such asphosphoric acidl In the course of my studies I have found that the action of zinc chloride on vegetable materials may be divided into 2 phases: y

1. A dehydratin action which brings the hydrogen content flown, say, in the case of peat, to about 2%.

2. A hydrolysis of zinc chloride which gives rise to hydrochloric acid with the formation of zinc oxide (ZnO). It is this oxide of zinc which furnishes the ox gen to decompose the residual hydrocarbons eft after the first reaction of the zinc chloride.

The dehydrating action of that reagent, is 35 advantages in avoidin" a loss of the carbon contained in the volati e matters, this carbon being. precipitated. While the latter ma initially be deposited in a form which stil contains hydrogen, the subsequent treatment will substantially eliminate the hydrogen and the carbon of the volatile matters thus precipitated will aid to build up the body of the active material.

As the decomposition of the zinc chloride, in the manner in which I utilize it, gives rise to highly corrosive gases, I prefer generally for the preparation of active carbons to use a mixture of sulphuric acid and phosphoric acid.

In general, in carrying out my processfI utilize finely ground vegetable substances or a substance from any other suitable source, such as decort-icated ivory nuts, peat, lignite, cellulose, wood or the like, or a mixture of two or more of such substances. The exact amount of each, of the acids to be used will vary somewhat depending on the material used and the type of carbon to be produced, and this can be determined by a preliminary test. Roughly, it may be suggested that 1 part of sulphuric acid (66 Be.) is mixedwith 2 parts of concentrated phosphoric acid and one part of this mixture is used with three parts of the raw material. Additional water is then added so that the mass can be worked into a paste. Upon the consistency of this paste will depend, in part, the ultimate physical qualities of the carbon, for the less water that is used, the denser will, be the final product, and it is an important feature of my process that the ultimate compactness can thus be controlled.

The paste thus prepared, is pressed into the form desired for the carbon, and here again the final compactness can be modified by the amount of pressure'used. A simple way of molding the material is by extruding it through aperforated plate. The resultin strings may readily be broken into pieces 0 any desired length, which are then dried at about 300 C. w

During the drying operation, the sulphuric acid dehydrates the organic matters and the product thus dried is in a geometrical form and contains, in the case of peat,about 2%.

hydrogen calculated on the carbon content The dehydration obtained by the sulphuric acid is such that there is practically no evolution of carbonaceous volatile matters, and consequently that there is in that first phase of the operation practically no loss of carbon;

After this first treatment the product is charged into horizontal retorts of ,the. ordinary. gas works type or any other type of closed calcining vessel, which permits the escape of gases. Under the action of heat the phosphoric acid is dehydrated and goes over into metaphosphoric acid, and when the temperature reaches about 800 (3., there is evolved PH, and then later PH, and finally phosphorus P. c

Since the phosphoric acid had thoroughly permeated the raw material, the rapid reac-' tions incident to the decomposition of the soluble and extracted by the reagents used.

l find it advantageous to recover the'phosphoric acid, and in order to do that I have used retorts which are connected-at one end to a combustion chamber in which the evolved products above mentioned areburnt, with the formation of phosphoric anhydrid. The latter is dissolved in Water and the phosphoric acid is thus regenerated.

It may be well to remark that the basic mineral matters, which may be contained in the vegetable products, are transformed into tribasic phosphates, and, consequently, the carbon obtained by the process described, will be absolutely harmless; and can, therefore, be utilized for the treatment of food products.

Besides, it is well to note that if an excess of phosphoric acid has not been used, the carbon after calcining will not need washing.

-The geometrical shape of the carbon is also a feature of value, as it permits of an efficient utilization of the apparatus employed.

When a solution of a metallic chloride, such as zinc chloride, is used in accordance with my process, the procedure may in general follow the outline already given (except that after calcination it is advisable to wash the carbon with hydrochloric acid and recalcine) and the hydrochloric acid evolved during the calcination may be recuperated by washing.

In certain cases I may use a mixture of hydrochloric acid and zinc chloride, generally kno wn as the Cross and Bevan reagent, or a mixture of phosphoric acid and hydrochloric acid.

By heating and digesting the raw material used, a good plastic mass suitable for agglomeration may thus be obtained even with coarsely ground substances or with raw materials, which may not, otherwise be easily agglomerated. I When these reagents are used the compactness of the product, as before, may be varied by modifying the consistency of the plastic mass or by modifying the pressure used in the molding operation. Further, under these particular circumstances, the compactness ofthe finished product may be varied by' making the digestion of the raw material more or less complete, for this will allow more or less of the hydrolyzable matter contained in the-raw material'to be rendered controlling the degree of dissolution.

The raw material (ivory nuts for example) ,is broken into small piecessay of sufficiently small size to pass through a quarter-inch mesh screen-and then is heated in the solution referred to. A certain amount of the hydrolyzable material is dissolved out and the compact-ness'of the product is, in this case, controlled simply by the amount of dissolution that goes on, which will of course depend on the time of treatment, the concentration of the bath and the temperature used.

' After the raw material has been digested to a sufficient extent, which with ivory nuts may be "shortly after the pieces have become translucent, the solution is drained ofi or extracted in any desired manner. The pieces are dried, and then calcined as already described, and'if necessary washed with an acid and then finally dried or recalcined.

It is to be noted that according to each -mthod which I have described, I control the degree of compactness of the final product prior to the operations during which the hydrogen is removed. As I have pointed out,

it is of great importance that these two phases of the problem be separately controlled,

for the hydrogen content should be brought down as much as ossible and at the sametime carbons of di erent degrees of compactness should be available, if one wishes to operate at maximum efficiency for different purposes. In general 'forthe absorption of light molecules a very compact carbon is desirable, whereas a much less compact carbonwill be more efiicient for heavy molecules.

evaporating down to dryness the solution which is drawn off after digestion of the raw material, and by continuing the heating of the dry residue until carboniting of the dissolvedsubstances has taken place.

This carbonized product may then be washed if desired and a second calcination may sometimes be necessary in order-to obtain very high class carbon.

The active carbon thus obtained will generally; be used in a pulverulent form; with the required degree of fineness, but I have also found tlratgranulated material for decolorizing or other purposes may be produced by dipping solid porous Isupports for/example pieces of coke or other suita'bldmaterial into the solution above referred to, prior to the evaporation and subsequent treatment.

It is to be understood that the term carbon is mostly used in the course of this specification as a usual technical term and is not intended to designate the chemical element.

It is also to be understood that the details which I have described in the course of this specification are intended to be illustrative only and are not intended to limit the invention.

Certain matters originally claimed in this case are now claimed in my cozipending application, Ser. No. 98,376, file 1926.

lVhat I claim is:

1. The process of producing active carbon which comprises permeating vegetable material or the like with a mixture of phosphoric acid and sulphuric acid, heating and calcining in a substantially closed vessel allowing the escape of gases ata temperature high enough to cause the phosphoric acid to decompose with the formation of phosphides.

2. In the process as defined in claim 1, in which the heating is continued until the evo- March 29,

lution of phosphorus containing ingredients table carbonaceous material and phosphoricacid, which product is substantially free from ingredients adapted to cause an evolution of phosphorus hydrogen compounds when said product is heated substantially above 800 C. As a new product, active carbon comprising reaction products of cellulosic material heated to at least 800 C. in the resence of a reagent of acid reaction comprising oxygen and phos horus in chemical combination, which ,pro uct comprises less than .3% of hydrogen.

6. The process of producing active carbon of predetermined density which comprises the steps of forming a compact mass of cellulosic material and a predetermined quantity of added liquid ingredients at least a portion of which demands a temperature of 800 C. to be distilled ofi, and thereafter calcining-such mass in a closed retort permitting the escape of gases, at a temperature of at least 800 C. 7. A method of pro ucing active carbon of predetermined density which comprises the, steps of forming a compact mass of cellulosic material and a liquid having ingredients adapted to distil off at various degrees of temperature, distilling off a portion of the liquid below the temperature at which the carbon in the cellulosic material will combine with oxygen, and distilling ofi an additional portion 012 the ingredients of such liquid at a temperature of at least 800 C. but in a retort which permits the escape of gases but does not permit inflow of oxygen containing gases, whereby combustion of carbon is maintained at a minimum.

In testimony whereof I hereunto afix my signature.

EDOUARD URBAIN. 

